# US 10,767,108 B2 · Perfluoroether-stabilized quantum dots

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- Number: US 10,767,108 B2
- Document ID: US10767108B2
- Status: Granted
- Kind: B2
- Application number: 15/745,749
- Filed: 2016-08-10
- Published: 2018-07-26
- Granted: 2020-09-08
- Earliest claimed: 2015-08-19
- Assignees: 3M Innovative Properties Company
- Applicants: 3M Innovative Properties Company
- Inventors: Paul B. Armstrong; Zai-Ming Qiu; Karissa L. Eckert
- Web page: https://patentgrep.com/patent/US10767108B2

## CPC

- C09K 11/025: {non-luminescent particle coatings or suspension media}
- B32B 7/12: using interposed adhesives or interposed materials with bonding properties
- B32B 27/08: of synthetic resin
- B32B 27/36: comprising polyesters
- C07C 319/18: by addition of thiols to unsaturated compounds
- C07C 327/28: having sulfur atoms of esterified thiocarboxyl groups bound to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
- C09K 11/02: Use of particular materials as binders, particle coatings or suspension media therefor
- C09K 11/565: {with zinc cadmium}
- C09K 11/70: containing phosphorus
- C09K 11/703: {with zinc or cadmium}
- H05B 33/14: characterised by the chemical or physical composition or the arrangement of the electroluminescent material {, or by the simultaneous addition of the electroluminescent material in or onto the light source}
- H05B 33/20: characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
- B32B 2250/02: 2 layers
- B32B 2250/244: All polymers belonging to those covered by group B32B27/36
- B32B 2250/40: Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
- B32B 2255/10: on synthetic resin layer or on natural or synthetic rubber layer
- B32B 2255/26: Polymeric coating
- B32B 2307/422: Luminescent, fluorescent, phosphorescent
- B32B 2457/202: LCD, i.e. liquid crystal displays
- B82Y 20/00: Nanooptics, e.g. quantum optics or photonic crystals
- B82Y 40/00: Manufacture or treatment of nanostructures
- G02B 6/005: {provided by one optical element, or plurality thereof, placed on the light output side of the light guide}
- G02B 6/0096: {the lights guides being of the hollow type}
- G02F 1/133614: {using photoluminescence, e.g. phosphors illuminated by UV or blue light}
- G02F 1/133615: {Edge-illuminating devices, i.e. illuminating from the side}
- G02F 2202/36: Micro- or nanomaterials
- Y10S 977/774: Exhibiting three-dimensional carrier confinement, e.g. quantum dots
- Y10S 977/818: III-P based compounds, e.g. AlxGayIn2P
- Y10S 977/824: Group II-VI nonoxide compounds, e.g. CdxMnyTe
- Y10S 977/892: Liquid phase deposition
- Y10S 977/95: Electromagnetic energy
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- B32B: LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- H05B: ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02F: OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

A composite particle comprising a fluorescent core/shell nanoparticle and a perfluoroether ligand bound the surface thereof is described.

## Claims

### Claim 1

A composite particle comprising a fluorescent core/shell nanoparticle and a fluoroether ligand bound to the surface of the nanoparticle of the formula:
Rf—[X1—R2—X2—R3(L)n]m
wherein
Rf is a perfluoroether group,
R2 is a hydrocarbyl group including alkylene, arylene, alkarylene and aralkylene;
R3 is a hydrocarbyl group including alkylene, arylene, alkarylene and aralkylene;
X1 is —CH2—O—, —O—, —S—, —CO2—, —CONR1—, or —SO2NR1− where R1 is H or C1-C4 alkyl;
X2 is a covalent bond, —S—, —O— or —NR1—, —CO2—, —CONR1—, or —SO2NR1− where R1 is H or C1-C4 alkyl;
n at least one;
m is 1 or 2
L is an ligand group selected from —CO2H, —SH, —P(O)(OH)2, —P(O)OH, —NH2—OH, and —SO3H.

### Claim 2 (depends on 1)

The composite particle of claim 1 wherein there are at least two L groups.

### Claim 3 (depends on 1)

The composite particle of claim 1 wherein R2 is a C1-C20 alkylene or an arylene.

### Claim 4 (depends on 1)

The composite particle of claim 1 wherein Rf is of the formula CaF2a+1—(O—CbF2b)c—, where a is at least 1, b is at least 1 and c may be a number from 1 to 10.

### Claim 5 (depends on 1)

The composite particle of claim 1 wherein Rf is of the formula —CaF2a—(O—CbF2b)c—, where a is at least 1, b is at least 1 and c may be a number from 1 to 10.

### Claim 6 (depends on 4)

The composite particle of claim 4 wherein each of subscripts a and b are 1 to 6.

### Claim 7 (depends on 1)

The composite particle of claim 1 further comprising a non-fluorochemical ligand bound to the surface of the nanoparticle of the formula:
R5-R4(L1)n III
wherein
R5 is (hetero)hydrocarbyl group having C2 to C30 carbon atoms;
R4 is a a hydrocarbyl group including alkylene, arylene, alkarylene and aralkylene;
n is at least one;
L1 is a ligand group.

### Claim 8 (depends on 1)

The composite particle of claim 1 wherein the ligand is of the formula:
Rf—X1—R2—S—CH(CO2H)CH2CO2H
wherein
Rf is a perfluoroether group,
R2 is a hydrocarbyl group including alkylene, arylene, alkarylene and aralkylene, and
X1 is —CH2—O—, —O—, —S—, —CO2—, —CONR1—, or —SO2NR1− where R1 is H or C1-C4 alkyl.

### Claim 9 (depends on 1)

The composite particle of claim 1, further comprising a fluid carrier.

### Claim 10 (depends on 1)

The composite particle of claim 1 wherein the core comprises InP, CdS or CdSe, and wherein the shell comprises a magnesium or zinc-containing compound.

### Claim 11 (depends on 1)

The composite particle of claim 1 comprising:
a fluorescent semiconductor core/shell nanoparticle comprising:
an InP core;
an inner shell overcoating the core, wherein the inner shell comprises zinc selenide and zinc sulfide; and
an outer shell overcoating the inner shell, wherein the outer shell comprises zinc sulfide; and
a fluorinated ligand bound to the surface of the nanoparticle, the fluorinated ligand of the formula:
Rf—[X1—R2—X2—R3(L)n]m
wherein
Rf is a perfluoroether group,
R2 is a hydrocarbyl group including alkylene, arylene, alkarylene and aralkylene;
R3 is a hydrocarbyl group including alkylene, arylene, alkarylene and aralkylene;
X1 is —CH2—O—, —O—, —S—, —CO2—, —CONR1—, or —SO2NR1− where R1 is H or C1-C4 alkyl;
X2 is a covalent bond, —S—, —O— or —NR′—, —CO2—, —CONR1—, or —SO2NR1− where R1 is H or C1-C4 alkyl;
n at least one;
m is 1 or 2
L is an ligand group selected from −CO2H, —SH, —P(O)(OH)2, —P(O)OH, —NH2—OH, and —SO3H.

### Claim 12 (depends on 1)

A composition comprising the composite particle of claim 1 and a polymeric binder.

### Claim 13

The composition of embodiment 25 wherein the binder comprises polysiloxanes, fluoroelastomers, polyamides, polyimides, caprolactones, caprolactams, polyurethanes, polyvinyl alcohols, polyvinyl chlorides, polyvinyl acetates, polyesters, polycarbonates, polyacrylates, polymethacrylates, polyacrylamides, and polymethacrylamides.

### Claim 14 (depends on 12)

An article comprising a quantum dots layer comprising the composite particle of claim 12 dispersed in a polymeric matrix binder, the layer between two barrier films.

### Claim 15 (depends on 14)

The article of claim 14 comprising from 0.1 wt % to 1 wt % ligand functional particles, based on the total weight of the quantum dot layer (dots, optional liquid carrier and polymeric binder).

### Claim 16 (depends on 1)

An article comprising a quantum dot layer between two barrier films, the quantum dot layer comprising the composite particles of claim 1 in a polymer binder.

### Claim 17 (depends on 16)

The article of claim 16 wherein the composite particle further comprise a fluorinated fluid carrier, dispersed in a polymer binder.

### Claim 18 (depends on 1)

A dispersion comprising the composite particles of claim 1 in a fluorinated carrier fluid.

### Claim 19 (depends on 18)

The dispersion of claim 18 wherein the fluorinated carrier fluid is selected from perfluoroalkanes or perfluorocycloalkanes, perfluoroamines; perfluoroethers; perfluoropolyethers; and hydrofluorocarbons.

### Claim 20 (depends on 1)

A quantum dot film article comprising:
a first barrier layer;
a second barrier layer; and
a quantum dot layer between the first barrier layer and the second barrier layer, the quantum dot layer comprising the composite particles of claim 1, the composite particles dispersed in droplets of a fluorinated liquid carrier, and the droplets dispersed in a polymeric resin matrix.

### Claim 21 (depends on 20)

The quantum dot film article of claim 20 wherein the quantum dot layer comprises dispersed droplets of ligand functional quantum dots in a fluorinated carrier liquid.